Bonded multi-layer structures



BEST AVAlLABLE COPY D. Comun-msi a:

428-451. XR 392199516 EX STRUCTURES 'LTI-LAYER BONDED BEST AVAILABL CQPX u ,zal ,Jiu

Patented Nov. 33, 1965 3,219,515 nonnen Meert-LM- f t TRUCTURES .David Stanley Cobble-dich, Decatur, itl., assigner to A. E.

This invention relates to a nrethcne primer. More particularly, this invention relates to a process of forming an in situ polymerizcd coating having goed adhesion to a substrate, which comprises the. steps of (l) providing a prepolyrner reaction product of organic polyhydroxy material having an average acid number or' from 0 to l0 and at least 1.2 equivalents of organic polyisocyanate per equivalent of organi: poiyhydroxy material, wherein said polyhydroxy material comprises a linear condensation polymer having a hydroxyl number or from 2O to 3D0 selected from the group consisting of polyethcrs and polyesters, (2) applying said prcpolymcr reaction product to u substrate, (3) dry-'ing said prepulymer reaction product, (4) applying an addition-polyrnerizable, resin-forming composition comprising a monoethylenically unsaturated monomer selected from the group consisting of vinylidene Compounds, half-esters of alpha, heta-ethylenicaliy tinsaturated dicarboxylic acids and mixture thereof, and a polyethylenically unsaturated material, wherein at least one substituent of said addition polymerizable composition contains Zerewitinot'i hydrogen groups, and (5) polymerizing said addition-polymerizab e composition in situ to bond it to said substrate.

During the last ten'or twenty years, various types of ad dition-polymeriahle coating and caulking compositions have been applied directly to various substrates and then polyrnerized in situ on the surface of the substrate. Generally this technique has been successful only whzre the substrate is suttleiently porous (en. wood surfazes or cinder blocks) to permit the partial penetration of the surface by the polymerizable composition. Subsequent polymerization of the composition results in the forniation of a physical bond between the porous substrate and the polymerized layer. Unfortunately, such techniques have not been too successful for caullling materials, such as those used in satt glazed-clay pipe joints and east iron pipe joints, and coating materials, such as those used on salt glazed clay tile and on steel, since no physical hond is formed between the substrate and the polytnerized coating. The poor `conding of in situ polymerized caulliing Compositions is compounded by the shrinkage of the caullting material as it polymerizcs.

In situ polymerirable coating compositions have been applied as thin layers to normally non-porous substrates, which have either been ahraded or primed with a primer to aid adhesion, with more or less success. llowever, such techniques have been, till now, unsatisfactory for permanently bonding in situ polymer-ized caulking contposlton to a substrate, particularly to pipe joints, due to -the stresses set up within the caullng compositions. Further as the size of the object to be 'caullusd increases, the more difilcult the adhesion problem becomes since the amount of stress on the bond increases with the amount oi material to be bonded. In :t typical case, where the hell end ot' a salt glared clay pip.: joint is caullled with a polymerizable cruilLing composition comprising aeout 150 parts silica filler and about lOO parts resin former, such as a mixture` of an unsaturated polyester and styrene, the circumference of the :stalking composition shrinks hy iront about 1L 96. ln many canes here a primer had been employed the caulltint; material separated from the pipe joint at the caullting material polymeri/ctl or shortly thereafter. ln other cases where apparently sueccssinl caull;ed pipe joints had been cast, the caulking pulled array from the primed pipe after shipment to the job site :md outdoor storage. This is zt relatively common occurrence during; the winter months, when the stored pipes are subjected to repeated freezes und thaws, since the contractions and expansions of the pipe joints under these conditions increases the stresses upon the bond. To the best cf my knouletige he two best primers available are (l) a vinyl trl:hlorosilane primer formulated by me which can lee used successfully as a primer for S pipe hut cannot hc used for i8 or 2-t" pipe (again because of the increased stress in the larger joint) and (2) an epoxy resin which has an unduly long dry time of about 3 hours. The term dry time" refers to the period required before a pril-nef? substrate can be coated with a top coat and still have the top coat adhere to the .sub-strate.

The object of this invention is to provide e. new, improved primer which forms a permanent, vreatlienresisrint bend between non-porous substrates and in situ poly recarized material. 'Ihe prim-:r of this invention is a urethane prepclymcr reaction product of an organic polyht'orory material having an average acid number of from o to ifi and at least L2 equivalents of organic polyisocyanate per equivalent of organic polyhydroxy material.

Other and further objects of the present invention will be apparent from the following detailed description taken in conjunction with the` accompanying drawing wit-:rein:

FlGURE l is a cross-sectional view of a pipe section;

FIGURE 2 is a view, similar to FIGURE l, ofthe pi section alter it has received the urethane primer of the prent invention;

FIGURE. 3 is a view, similar to FIGUREi I and 2, illustrating the manner in which the in situ addition polynxeriaable caulliing is cmplaccd; and

FIGURE 4 is a view illustrating the pipe section with the polytnerized caulking composition applied thereto and the mold forms removed.

In referi ing to the drawing, and with particular reference 'to Ptoutus 1, a length of pipe 1o having a beu mi 11 and a spigot end I2 is illustrated. Bell end 1i is equip pcd with a radial flange portion i3.

In accordance with the present invention, a urethane prepolymer reaction product, the preparation and com position of which are more fully explained below, is ap plied to the outer surface 12a of the spigot end of pitre section l0. The primer is preferably applied in a rbh laye.' I4. Similarly, at the bell end l1 or' pipe cad l0, a primer layer l5 is applied tothe radial .flange 13 and isser wall lle. Primer layers 1li and 15 are then permitted to dry.

After drying` a ring i6, previously treated with a meld release agent, is placed on the radial flange 13 thereby forming a mold 17 betas-:n ring 16 and primer layer I5 at the l-:ll end 1l. As is shown in FIGURE 3, spigot end 12 ir; supporttd on a has.: 18 so that a ring i9 can be placed therearound in surrounding relationship to provide t. meld 20 between primer layer 14 and the inner surface lill of the ring I9. If desired, ring 19 can be formed in sections for facilitating removal.

An in situ audition polymerizahl compound is tiert prepared. in the manner explained below, and poured into the respective molds 17 ano It). As oon as the addition poly'nzet'irabte compound harde-nf' '-nd bonds to the primer layers 24 and l5, the rings li :wi lq are removed. J.;- cortingly, as is shown in lilGUttt. 4, the hell cnd of tire pip-z vril trie provide-l uith a nztzltitayeted caulkiag comp-o ittou hielt iucludss :t polyuretlume primer layer l5 aad an in situ polyutcrired layer 2i handed thereto. Similarly, hell end l1 of the pipe itl in lutlcs a polyurethane prim-:r layer l-l and n similarly handed in situ pelyfnetit/.ed layer 22. The caulked pipe sections can he joined together in i t r 3 the field in ac'c irilaiice, with conventionally lcnown tech-- niques.

The urethane primer of this invention comprises three essential ingredients which are: a polyisocyanate, a difunctional, essentially linear polyhydroxy condensation compound having a hydroxyl number ot from about 2O to 100 and apolyhydroxy compound having n functionality of 3 or more. Th'. polyisocyanate apparently functions in atleast 3 ways which are: (l) reacts with the polyhydroxy materiel oi the primer to forni a high molecular weight polymer, (2) reacts, with Zcrcwitinot'f active hydrogen groups oi the in situ polymerizale layer to chemically bind the top layer to the primer, and (3) reacts with the suhstrate in a manner sufficient to bind the primer to the siiostrate, probably by chemical bond. The essentially difunctional linear polyhydroxy condensation compound having a hydroxyl number of from about 2O to l0() gives the primer layer flexibility and elasticity while the polyliydroxy compound having a functionality of 3 or more gives the primer tensile strength. The omission of any one of these ingredients results in a primer unsuitable for most purposes.

In greater detail, the essentially linear diiunctional condensation polymer has an acid number of from about O to l0 and a hydroxyl number of from about 20 to l'OO, piet'- erably from 40 to 80. These linear condensation polymers include polyethers prepared from the condensation of ethylene oxide, proriylene oxide, tetrahydroi'uran, ete. alone or with various glycols and hydroxy terminated polyesters. The hydroxy terminated polycsters can bo renaretl from l or more aliphatic dicarhox 'lie acids, such I' t as adipic acid. malonic acid, succinic acid, methyladipie acid, maleie acid, thiodipropionie acid, diethylethcr-di carboxylic aedsebaeie acid, saber-ic acid. etc. and l or more glycols, such as ethylene glycol, 1,2-prcpylene glycol, i,3propylcne glycol, 1,3-butylerie `glycol, 1,4-butylcne glycol, 1,6-hexanc diol, methyl hexane-1,6-diol, l,4-butcne diol, diethy ene glycol, trizthyiene glycol, thiodiglycol, 2, 2dimethyll,3 propylene glycol, ete. Ilydroxycarboxylie acids and lactones can also be used to prepared these linear polycsters. Other bilunctional reactants which are complementary tothe acids and glycols can be used in smaller proportions, such as phtlialic acid, terephthalie acid, pphenylcne diamine, aminopropanol, ctc. Iilowcver, the preferred linear; essentially difunctional condensation polymers are polyesters of adipic acid and ethylene glycol and/or 1,2-propylene glycol having a hydroxyl number of from about 40 to .9.0. These linear, essentially difunctional polyhydroxy condensation polymers and the polyhydroxy material having n functionality oi at least 3 are present in a weight ratio of about 4:1 to. 1:4, preferably from about 3:1 to about 2:3. When the linear, essentially dilunctional polyhydroxy condensation polymers is present in a weight ratio higher than 4:1, the primer layer has low tensile strength white at a ratio less than 1:4, the primer is not sufficiently flexible. In either case the bond ironie-d between the substrate and top layer is unsatisfactory for cnullcing applica' ons.

The polyhydroxy matt .al having a functionality of 3 or more can be a relatively simple polyol such as glycerin, triinetliylol propane, trimethylol ctiiane. pentaeiythritol, hexane triol, il,l\i,l\",ll'tctraltis(Z-hydroxyethyl) ethylcncdiamice (this compound also has cati-.lytic properties iis described below), cte. or a condensation product of one or more of there pnlyols with one or more ot the aforementioned linear polyctlier-forminr: reagents nnd.'or poiy ester Parents. Generally the preferred pnlyhydrorty nia terizls having n functionality of :it least 3 are polyester condensation pied-.iets or' a trial (particularlv tiinieihylnl ethftne or ti'inetliyltil propane) with n tlilunctional acid (pt ii-iiiilarl :iitiiiie :ici-.ll iiiitl a ttiiunctirinal glycol (particulaily ethylene glycol :ind/or l,1-prupylene glycol) having hydroxyl number ot from about 120 to about 225 :netocio BEST AVAILABLE COPY and an acitl number less than i0, These preferred hydroxyacrminatcd polyesters, particularly those liavii 'z a hydroxyl number ot from about lZO-ttit), torni sommi-itat flexible urethane coatings when used hy tiittniselves and accordingly complement the ilexilrilixing ciiect ot the cs- ;entially li car difunctional pelyctlicrs and polyestcrs. lt is within the scope of this invention to prepare a mixture of essentially linear difunetional condensation polyesters and triiunctional condensation polyesters at the same time by the choice of suitable proportions of reactants and reaction conditions.

he polyhydroxy component of the urethane primer can also include low molecular weight diols, such as ethylene glycol, ci'icthylene glycol. N,Ndi(hydroxyethyl)`-n.ethyl amine ',this compound also has catalytic properties as explained below), without adverse effect on the. bonding7 strength ofthe primer.

The rolyisncyanates used in this invention can include aliphatic and aromatic diisoeyanates such as tetramethyienc cliisocyanatc, pcntamcthylcne diisocyanate, ii-: ;:trrietbylene diisocyanate, tiiiodiprop'yl fliisocyaiinm, iltcriylene diisocyanate, CILJOmpheiiylene disocyanatc, toluene diisoeyanate, naplithalene diisocyanzite, durera: clisoeya nate, ctc. The aromatic diisocyanates and par culnry toluene diisocynnate, which is available commercially in mixtures of the 2,6 and 2,4 isomers, are, preferred. the isocyanate groups in the 2,6 position of toluene 2,6d-

isocyanate, and in the 2-position of toluene .'.,-tdi anate are sterically hindered and accordingly com; containing these isomers in the proper isoc}'anate-to-liy- -droxyl ratio have a relatively good pot life.

For converting the polyhydroxy material into ty;

'When the isoeyanate-to-hydroxyl ratio is over 2:-"t there will even remain .some free diisocyanates in the mix. The more chain units which are linked together ant. the fewer the number of free isocyanate groups, the shorter the pot life ofthe primer. While acceptable bonding has been obtained in the laboratory using printer corzipositions having a low ratio (eg. 135:1); such compositions do not have the necessary pot life for use by untrained routincers under varying hui'iidity conditions. In open containers water from the atmosphere readily reacts with isoeyanate groups forming a urea linkage between two isocynnzite groups. Accordingly in order to insure that an open container of primer has a pot life of at least 4 hours, I prefer to use an isocyanate-to-hydroxyl ratio of at least 2 or 3:1.

The urethane primer of this invention usually and preferably contains a catalyst, such as a tertiary amine, which may or tay not contain hydroxyl groups, or an organotin compound. From a cost point of View tertiary amines, such as N,Ndl(2-nyflroxye ttyllineihylaiuine, dicthytcyelohexyl amine, I\I,N,s",N-tetral is Z-hydrortycthy1) ethylene diamine, N-etliyl morpholiiie, methyl pipcridinc. diniethylpiperazine. tribenzyl-ainine, tetramethy't-diaminotlipropyl ether, ete. are more tlcirtible than the orgaiiotin compounds. The preferred tertiary amine catalysts of this invention are N,Nili-(2li,\-lroxyethyl)methylainine and dietliylcyclolieityl amine (also called hexziliydrotliethyl uniline). Urethane primers using either oi these catalysts have a tli'v time oi about 5 to l5 minutes. On the other hand primers b:is:d un N.N.N',N'vtetruistl-liytlrnxyctliyl )ctiiy iene diamine have considerably longer ilry times of about lS-'Jtl hours.

'l'he active inixrecliciits of the urethane primer ot' this invention are dissolved, in a relatively volatile anhydrous following: ccllcsclve l .ctonc. ethyl acetato,

cadmium red, iron oxide red, cadmium orange, molyedate orange, cadmium yellow, llama yellow, iron oxide q.cllmv,

- chrome oxide green, piitlxalocyanine green, phthzrlocyanine blue, ultram-urine blue, carbon black, hone blacl'., iron oxide black, titanium dioxide, litlropone, antimony dioxide, ummr, iron oxide brown, etc. can. be added to the primer. The pigment ztilou's the user to tell by inspcction whether the substrate to be coated has been primed or not. This is particularly useful when a primer which has along dry time is employed.

All of the ingredients of the uretaane primer can he orinulatcd together and then shipped. However, it is generally preferred to mix all the ingredients ofthe primer together except the diisocyanate and have the user blend in the o'iisocyanatc. While the former method is more convenient for the usc-r, the latter method insures. that the primer has good not life at the job site.

1N SITU POLYL'IERIZABLE COMPOSITION The in situ additiompolymerzable resin-forming ccmpositon of this invention comprises at least two com- Aponents which are: a monocthylenically unsaturated cornpounti and a polycti'iylenically unsaturated compound, wherein at least one substituent of said addition polymerizahle composition contains activo Zerewitinot hydrozen groups. The active Zerewtinolf hydrogen groups are necessary in order to insure the formation of a.

chemical hond between the primed substrate and the in situ polymerized composition. ,i

Th; polyethyle ically unsaturated compounds include the elhylenicaily unsaturated polyesters which are the reaction product of 'one or more polycarboxylic acids and one or more poiyltydric alcohols. Such products are terminated 'oy hydroxy and/or carboxyl groups and accordingly contain active Zerewitinot'r' hydrogen groups. One or more of the components of the polyester must be ethylenically unsaturated, preferably the polycarhoxylic acid component. Typical unsaturated polycarhoxylie acids include dicarboxylic acids such as fumarie acid, malcic acid, tnaleic anhydride, itaeonic acid, citraconic acid, etc. Oi these maleic anhydride and fumarie acid are preferred. Typical saturated polycarboxylic acids include dicarboxylic acids, such a phthalic acid, isophtlialic acid, succinic acid, adipic acid, suberic acid, sehacic acid, azelaic acid, ctc. Typical polyhydric alcohols include glycols, such as ethylene glycol, diethylcne glycol, tricthylene glycol, tctraet'nyleae glycol, propylene glycol, dipropylcne glycol and hexylene glycol; triols, such as glycerin, trinzethylol ethane, triorethylol propane and hexane triol; pentaerythritol; etc.

When an ethylenically unsaturated polyester is used in a caul'ning composition it is usually desirable that the polyester be n flexible poljtcstcr, preferably, or a semirigid poly'cslertltlough mixtures of these may be used wnh rigid rol)'e"'c-is. lilexihlc poly-esters form copolymcrizntes with yi yiidcnf; monomers (preferably styrene) having an elastic nicu'ulus of from about 10 to about 10,000 psi. while sentirigid polyesters form copolymers having an elastic modulus of from about 10,0% to 150,000 psi., isc. less than about 1503300 psi. ln addition, rigid polyeftcrs, whicr form corel; rizates lening :in elastic modulus of from about 150,000 to 600,000 psi. can he used as the cole polyester in in situ polymcriz'ctl mating count/:sillons in addition to thc i' .tiule and semi-rigid poly-esters. (lent-rally, the non-rigid poly- -iln from about 95-5tl mole percent saturated dicarlioxykc acid und correspondingly 5--50 mule i-.crcent alpha, heta-cthylencally unsaturated dicarboxylic acid, while the pelyhydroay component is principally a glycol.

BESI AVAILABLE COPY Usual? no lon-iter the chain length of thc glycolx or salumi-:fl dicarboxylic acid components maltirg up the p-:ljfc moieties?. e {i1-c polyester. Aromatic com ,non nts fa'vliirh are considered saturated materials for the purpose this invention), particularly phil` are not as effective as long chain saturated all;

. lowering the elastic modulus of a copolymer. However,

the low cost of phthalic acid usually makes it a desirable cornpor.-n t.

The ezhylcnically unsaturated polyesters comprise from about 3D to lO weight percent of the in situ polymerizable resin-forming components. The remninia" '50 to 23 weight percent of the iu situ polymerizahle resin-forming ingredients comprises :t yinylidene monomer selected from mcnoyinyl aromatics, such as vinyl tolse-1c and styrene, al'tyl esters of alpha, hcta-ethylenically unsaturated tno-:tocarboxylic aci-ls, sus as methyl ntezizaaryiate, methyl acrylate, ethyl acrylatc and 2-etliylizsyl acryiatc, vinyl esters sich as vinyl acetate and propionate. The preferred t'inylidcne monomers arc styrene and vinyl toluene. 1i desired, various other diunctional materials sach as diallyl phthalate may be added to the composition.

Another class of polyethylenic-.ally nnsatentted :nateriats lich can be used in this invention .include acryloaysubzititutcd fatty-acid esters having an average of at least 1.3 acryioxy groups per molecule. A number of the" acryloxy-substitutcd fatty-acid esters :Je disclosed and claimed in application Serial No. 126,394, 'led lune 8. 1961; application Serial No. 119,33- flied lune 26, 1951, and application Serial No. 119,346, filed lune 26, 1961, now Patent No. 3,125,592, which are continuations-'t-part of forfeited application Serial No.

800,071 filed March 18, 1959; application Serial No.

' 167,153, filed January 18, 1962, and application Seria] No. 167,154, filed January 18, 1962. 1n general. these materials form. films that retain somewhat more taci; than the aforementioned polyesters and accordingly, they are preferably used in caullrirlg compositions when: their inherently superior exibility characteristics can oc best utilized.

In somewhat greater detail the acryloxysu'stituted fatty-acid esters have the structure:

t l l. P.o-o l LH vhcrein each. R is independently an open chain of from l0 to li carbon atoms containing at least one Segment ,in said own chain having the structure X is hydrogen, halogen or hydroxyl; R, is Lydrogcrr O Loy when R, is hydrogen, Rg is hydrogen, alkyl ci .from 1 to 4 carton atoms, alltoxy of from l to 4 carbon atoms, halo-vien, phenyl, benzyl or ll ctn-o o? when R, is

BEST AVAILABLE COPY PROCESS A typical method of employing the primer or' this invention comprises adding diisocyanate to the various other components of the printer composition (anhydrous solvent, polyhytlroty material, catalyst and pigment). The resultant couniosition can be applied immediately as a thin laye directly to the substrate. However, l prefer to allow the printer composition to to through its e. thernt in the Container and then cool before applying it to the substrate. ln either case the primer is extremely el`t`cctive. However, it has been found that as the primer apes (uithin its pot life expectancy) its subsequent bondf g strength improves. As a practical matter, however, little attention is given to thi.` by the practitioner in the ricld. After application, the primer is allowed to dry for from about minutes to .several days, depending upon the catalyst as explained above. Then the in sito polyrnerizable composition is applied tothe primed surface.

when :he primer has been applied to the spigot end and bell end o a :lay pipe joint, the spigot end is placed on a suitable flat surface. The spigot end is surrounded by a carefully dimensoned ring, which has been treated with a mold release agent, such as polyvinyl stearato, petrolatam, carbowax, etc., forming a mold between the pip: and the ring to receive the joint forming material. Correspondingly, a ringY is placed in the bell end. In each case, the ring and pipe end are essentially concentric and form an annular mold between said ring and pipe end. The polymerza'ole caullcing composition comprising the polyethylenically unsaturated material, mono cthylenicaily unsaturated material and filler mimd with one er mole free radical catalysts, such as dimnzoyl peroxide, methyl ethyl ketone peroxide, hydroxyheptyl peroxide, ctc., is then poured into the mold to the proper height to form the joint deancd by the molti. External heat may be applied to polymerize the resin forming materials. However, it is `generally preferable to add one or more accelerators (or driers) such es cobalt napluhenate, cobalt octoate, dimethyl aniliae, etc., to t'ne polymcrizable material in order to get a room temperature cure.

When a room temperature cure is desired, it is advanag-:ous to employ a mixing gun which is fed by two tanks. The first tank contains all the components or' thc polymerizable composition (catalyst, polymerizable monomcis, filler, ete.) except the accelerator which are either mixed together in the tunic or ia separate compartments while the second taal: contains all the components o the polymerizable composition (includingy the accelerator) except. the catalyst. All the components are mixed in the mixing gun and flowed at a steady rate from the gun into the molds. Usually the polymcrizable compoition will set to a solid muss which is substantially bonded to the pipe in from about 3 to about l5 minutes. At this point the molds are removed from the pipe.

Essentially the sante technicpte is employed for coating using any of va :us types ol apparatus such as spray guus, curtain centers, ctc., to apply the individual legers. Alternatively, the extern-:tl layer to be bonded to the subs-trate may be cest in place using a suitable mold very much in the manner dc-cribed above.

The following examples are merely illustrative and should not he cor-.Arnett as limiting the seep: of the invention. ln the examples, the word "parts" reifer: to puits by weight.

.'a the examples to follow structural clay products are cmaoyetl as the subntrate lince their enteral-ly smooth .surfaces present tt particularly s: ete bonding, problem,

2,-ltoluene diisocyanate and 20 part'. .fftoluene diisocyanate) with parts if a mixture of 2, p uls ethyl acetate (urethane grade), -l8 parts i'. ll diethanol amine, S0 parts CP. cadmium medium red 1,-300 pigment, 283 parts Multron R-IZ (a ruodxately branched polyester basing an acid number 4.0. l roxyl number of from 158 to 170 and an equivalent weight of 337, which is believed to be condensation product of trimethylol propane, propylenc glycol, ethylene nlvcol and adipic acid) and 432 parts ltlultron-lS (a pol-,ester hat ing an acid number of l 5, a hydroxyl number of from 47 tu 63 and an equivalent weight of 9213, which be' lieved to 'oe the condensation product ot' et ylene. glycol, adipie acid and a minor proportion of pitthcilie acid). The primer composition was allowed to stand for about l5 to 30 minutes during which time tir: pr' er eX- cthcrmed. The primer was then applied as a thin layer to the bell end and spigot enel of an 845:21 diameter salt glazed clay pipe. After the primer was prmitted to dry for about l0 minutes, a ring was placed in le eetl cad of the pipe and a second ring was placed around the spigot end of the pipe. The rings had ieei previously treated with a mold release agent, comrising 30 parts by weight lyrax A (u poljt'vinft-l steer e polymer) and parts by weight of Skeliysolve C (l: .1

A caulicing composition was prepared in the following manner. Sixty-seven parts of 2-ct 'hexyl fumfiryloxy hydroxy soybean oil (containing free -ethylilexyl hydrogen fumar-ate), 2?. c-zus styrene i l1 pans Z-ethyllcxyl acrylate '-.vere blended with lS pens of silica flour (Sterling 200 mesh), 0.(1 e't ifi-nachm@ part methyl ethyl ketone peroxide and one bal bis-l-hydroxy cyclohexyl) peroxide vez: added to one hall oi the aforementioned composition., One part ce 'oult naohthenute and 0.5 part dimetlulat .iti-z was added to the other half of this composition. 'l"M two compaitions `.vere thc-n mixed together and poaiett ir-cthe bell end of the pipe. 'The furnttrylozty h tdr ,xy so; bean oil product gellcd in about 2V: to 3 minutes. rtly thereafter, the ring was pulled from the bell und. The joint now had a perfectly cylindrical surface. A similar cornposition was prepared and applied to the Vigot end ot' the pipe with essentially the same' results.

The bond between the clay pip: of the tyre described was tested in the following manner. The pipe was sealed in water for 4 hours at room temperature, then ues p. in a food t'reezer at 0 F. for 16 hours, than removed from the food freezer and equilibrate-J for 4 hours at room temperature. After 30 cycles there was no sig of any deterioration in the bond betueea the pipe and the caulleing composition. The aber: trcezothaw cycling, was designed to simulate outdoor storage during the winter.A

The 2-ethyi`1exyl fumarylorty hydroxy soybean oil was prepared as follows. 'One mole of mal: ihytride (9d gram-ft was weighed into a llc-.slt equity.: ,i `.tith a stir er, thermometer, condenser and dropping heated to ll0 C. Otte mole of 2e; grams) was added slowly (approxim through the dropping funnel while uren-i.. ng the re:c tion mixture :it lill" C. Tte lompe; :e pas maiatizin-:d at C. for forty minutes :titer ttt: a lethylhexanol was complete. The res2:.-.r.t hut'tester of maleie acid was isomeried by ltcatii :.1 11G" C. for l2 minutes in the presence of sixty-chart :retiths of a gram of phosphorus trichluride. linut:- hereafter, lill prisms ot' epoxitlized yb-can oil ccf'. :ne 6.4% by eight of oxirane (l equivalent) and 0.3? gr. ot busi: zine sultoxulate forti allie-hyd: (0.0013 er.';`..-l \..as added to the hail-ester reaction vessel. Th: reactants ttf-lt: maintained at C. until the miran.- \..lue (by llltrzic-:tic acid titration) was less than 0.!0 :i ,f'g. (4t) tA utes). The product after cooling was :i \iscous, clear,

.tO minutes) li. pale yellow iiuuid having on a nverar'e two lumriryloxy hydroxy groups for cash rnoieeule of epoxidized soybean oil reacted. he produ-:1t analyzed:

Free 2-ethylhexyl hydrogen fumarale (percer t by wt.) 20.5 Saponication ..4 meq./g- 5.92 Hydro\;yl ...nasty/g- 1.50 '[nnsisomer .,percent-- 93 Viscosity at 25 C. f.:p -?.8,SO0

four ine-ies propylene glycol, seven moles ethylene glycol and 10 moles adipic acid.

Example Il Example I was repeated with essentially' the same results except that the primer used consisted of i parts Mondur TO-SO and 60 parts of a mixture consisting of 432 grams Multron R-lS, grams hiullron R42, 80 grams CP. cadmium n'eoiunt red #300 pigment, 72 grams methyl diethanolarninc and 2,428 grams ethyl acetate.

A series of salt glazed joints were caullsed with the composition of Example I using the primer of this example varying the age of the primer and the dry time of the primer on the pipe. The age. of the primer was caleuiated from the time the primer exothcrmed. The results are set forth below.

Age ol primer Dry time Freeze-thaw cycles lo failure nltinl. minut-es.. 30 im 30 nitnues.. 13 Do l hour 10 ].\o. Bhours l1 Four hours... t() niinuter,--. 3O 1) 30 minutes.... 18 l hour.. 28 3 hours t8 `Stypol 3018). Stypol 3013 is believed t be 30 to 35% by weight monomeric styrene and 65 to 70% by weight polyester (composed of 110 parts phthalic anhydride. 35 parts diethylme glycol, t8 parts tall oil fatty acid esters und 7 parts mal-:ic anhydride). A eaulkini; composition was formulated from this polyester composition using 100 parts polyester, 140 parts silica llour in n catalyst systcm composed of Lupcrsol DDM, cobalt naplulienule and dimethyl aniiine.

Exam/)Ic IV Example I was repeated with essentially thc same to gunt; en -epi the` primer used consisted of lll parts Monnu VD-Sti and 6() parts of u mixture consi-ting'. of 72 {..rts' Multron R-IS, $8 parts VMultron R-l2, 15.7 parts di- BEST AVAILABLE COPY etiiylcyclehexylamine, lt.7 parts diethylene glycol and Llll-l parts ethyl acetate. he fieshiy prepared primer' composition was applied to the .salt glazed pipe :and rdlowed to dry for tl) minuies. The cziulkcd pipe jo.nt was cut axially after 10 freeze-thaw cycles, without any sign of deterioration in the hund between the caullting cornpositlon and the clay pipe.

Example V Example I was rep-:ated with essentially the same results except the primer used :onsisied ot 10 parts Mondor 'TD-SO and 7S parts of a mixture consisting o 2 parts Muitrop R48, 4S parts Muitron li-l2I 15.7 parts dicthylcyelohexyl amine and 404 parts ethyl acetate. The salt glazed clay pipe joint was raulf Id alter a lll minuto dry time. The pipe joint was cut atei y :titer IO from@ thaw cycies with no deterioration in the hond betr/ee. the eaulking composition and :he pipe.

Example VII This example illustrates the use of a urethane primer4 having an i8 hour dry time and an extremely low ratio of iseeyanate to hydroxyl groups. The primer used consisted of 30 parts Multron R-IR, SO parts hultron 'r1-l2, 30 parts acetone, 6 `arts NARN',N'tetrakis(Z-hydrofryethyl) ethylene diamine, 3() parts ).Zc-ndur TD-SO, and parts toluene. A bond Letwecn the salt glazed clay pipe and the caulking composition of Example I failedy after 27 freeze-thaw cycles.

Example VIII This example iliitstrates that the primer Composition of this invention musi have at least one linear difunctional resinous component. Example VI was repeated using a primer comprising 30 parts Multron R-VZ. 5U parts acetone, 6 parts N.N,N'.t\"tctral is(hydroxyethyl) ethylene diamine, 30 parts Mondur YD-S0 and l5 parts toluene. After an IS-hour dry time, the salt glazed clay pipe vas caulked with the composition of Example I. The hond between the caulking composition and the clay pipe joint failed on he 5th freeze-thaw cycle indicating that it was unsuitable for storage above ground during the winter months.

Example IX Example I was reeattd using a primer consisting of 30 parts Muliron R4H, 20 pars Huttrop ll-l2, 50 parts ethyl acetate. 2.5 parts melhyle'cthannl amine, 2S parzs Mondor "KD-SO and parts :ottiene The salt glared clay pipe was caullacd after a 3 hour dry time and the joint had not failed alter freeze-thaw cycles.

Iir'nmplc X Example I was repeated using a primer composition consisting ol' 3() parts .\ii'l:ron lv-l'a. 20 parts Multron llt-l2, 5l) parts ethyl neetut'r. :ia-d 5 parts niethyldiethnnol amine, 30 parts Muntlur 'ID-S17 and .25 parts toluene. After :t ttl-minute dry time. the salt played clay pipe was caulked nml the hund Mtv-teen the culling :md the pipe had not failed idler 30 fteeze'thftw Cycles,

Example I was repeated ith essentially the san-.e re- `mits except that the 'l-ethyihcxyl famaryloxy-hydroxy pared 'ny the technique dmcriucd in lruunple I except that 0.7 tnoic ol tnonodetry! lltniirrtte was reacted with l equiv- :tlcrtt ot" epoxidized soylierm oil.

limi/:plc 'II Exemple l wrm repented with esoentizilly the sinne rcsults 3:62p? thttt the Z-ctltylltcxyl funint'yloxy-hyt.lroxjf soyllr-r-:t oil was replaced with 67 parts ntehylittnyl tum:- rylo\ \'l`.ydroxy .'oylL-:m oil whir: vos gueym'ed oy thu techni-quo described in l :nl: l ttzlng l infile of methyl- :tntly :alcohol in place of l nien: etliyllzcxnnol.

:sample XII! Exemple I was reperite-d with essentially tltc same restilts except thztt the join. t'ouiting con.rio:.ition was baud on u metltylotnyl fum:trylr ..aychloro soyboztn oil. The 4- m-:thyl--pentonol (methglnmyl alcohol) ltnnctryloxy- 14 rute in n 10C?.- ny weight solution of butyl :testate was Sptuytl n t5@ printed tric. 'lfm polyter errnponltion wus allowed to burin to :ure :in l utter l niinttteS, :t seeond coztt ot the struc compo itlon was sprayed on the Two hundred grants of soyrcnn oil und 0.03 gram of plncthfxy phenol w-:re added rapidly to the vessel and the temperature wos adjusted to C. Gne mole of tertioty butyl hypochloritc was fidi-:d over .'xty minutes while mitintuining the cxothermie reaction :it (i5-70 C. The rencticn tcrnper'zttttre wes maintained for :in additional 30 minutes before vriendin Milling luy-proline? tertiary butyl alcohol. The product was clear, paie-yellow liquid having u viscosity of 5,030 ccntipoies :tt 25 C. and :tn average of about 2-tuuurylexy groups per molecule :rnd about 20% by weight of :nett-.y :tmyl hydrogen furnurate.

Example Xl V Example Xll( was; rammed with essentiallythe some results except that n 'fl-ctltylh-:xyl fumoryloxy-chlcro soybean oil zu employed. Tlv: 2-ctiglhcxyl t'umzlryloxychloro soybeit t oil wits prepared by the method described in Exitmtlc Xlll c"7ept that the 0.8 mole of metltylamyl alcohol was replaced by 0.8 mole of 2etitylhexnn0l.

Enz-.tuple lll was repented using a polyester cuulking compt\,:ir\n bosed uren :t polyester sol/.l 'oy laico Chemical Componi', formerly rolled Celntt `e mii-44". The polyester composition comprirct. 3G to 35% by weight styrene :ind n polyertcr hnsetl upon phthttlic :reid und rnuleic acid. The cnul-:lng comp dition contained puits resin forming ingle nt. lll() parte silica tlot'r, Lupen-ol DDM colwul' nftphtmnttt; und dimethyl aniline. The Cuttlldng had eicellen: :adhesion to the sztlt gland clay pipe.

li.\' .tntiully the some rcrults were ohtnined hy replocin; the :llove polyexter with :t l): Soto rf\lye\ter:.tyrent -'.otn powition No. lO--274 bus/.J upon plithulic :xvid und .nnleic und.

tlrst ccnl. ttor one hour, the gl; -d tile wxs placed in un oven :tt F. The pizzi-named coating had excell-cnt odlteyion to the unglozed Clny tile.

Elscntinlly the sante results were obtained by allowing the second sprayed cout to dry overnight. at room tcmprrnturc.

Since runny embodiments of this invention may be made :intl .since many changes may be mode in thc ctnlwodirnents duxroed the foregoing is to be interpreted as illustrative. only :ind rny invention is defined by the claims appended hereucr.

l ci: im:

1. The method of forming a bonded multiluycr structurc including a sulwtrnte and on in situ polymerirni ltiyer, uhicn comprises th: atop; of (l) providing; :t prepolymer retti-tion product or un organic polyhydroxy' motorini having :m average :cid number fre-:n G to lil :ind at least 1.2 equivalents or' organic poiylsooyonut. per equivalent o.' organic polyhytlroxy material, u'l ere-io Suid organic pfvlyhydfoxy mutt-rio! comp-rises :tn esvntifllly difurctionnl linear condensation polymer l-e hydroxyl number of from about 10 to litt) sclrctcu trom the group consiiting ot' polycthzrs, polycS-tcrs and ri tures thereof, (2) :tpplying soil prt-polymer i product to Suid substrate, (3) drying'` said propo reaction product, (At) applying on seid dried regt. product on in situ addition-pol;mcrizahle resin for ng; composition cornpriling a polyethylenienlly unsaturated motorini :ind a monoctlzylcnicztlly unsaturated ruote-rial selected rtrrt the group cons' 'ng of rnonoyinyliderze compounds, hult'esters of lplzuletm:thylenicztlly unsotttruted tlic::;lfo','liu acids and mixtures thereof, wir" Yin :it least one of said unse :untel materials conf' tive Zer:.'itinot hydrogen groups, and (5) poly inerti ing xuid :idditiompclgfmcriznble compoailion to bond the resulting; polymzrizetc to said substrate.

2. 'Pte tncthol of claim l wherein said in situ oddition-polyrneriz1t :te compoaition comprises an ethylerticr-l- 1y umuturutcd poly-ener and a monoyinyl aromatic oompound.

3. 'll'.c method of claim 2 heroin Suid polyisocyanute comprises a diisocynmtte und smid organic polyhydroxy material comprics from l to 4 forts by weight of :m essentially difunctionnl linen condensation polymer how .lng` a hydroxyl number of from 20 to l0() selected from the group consisting of polycthers, polyesters and nii);- tures thereof and from 4 to l ports by weight of :t polyhydroxy organic mztterinl having at least 3 hydroxy groups.

Il. The method of claim 3 wherein said prepolymcr reaction product cou-:prints :t tertiary amine ezuttlyst.

5. The method ot claim 4 u'l-.zrcln said tertiary amine catalyst is methyl diethzmol amine.

ti. rThe metilol of clztint 4 wherein Suid polyltydroxy nttteral contpries from 3 to l ports oy weight of en elsentinlly dituut'tontl linear cendermlion polyertcr of un olipl ntic dicrtrl'nxylie .'xcitl :lnJ :tn oliptutie glycol, snitl polyester having un hydrorijl number of from 20 to 100, :ind from about 2 to 3 perl; 'oy weight of polyhydroxy organic compounds ltr-'Enq :it legst 3 hydroxy-t group centplhirrg :t cunJen-rition polyeter of n polyhydric alcohol having :it lernt tl'trc: hydroxyl groups, un aliphatic glycol nud .nn nlinhetic dfxtrhoxylic ttcitl.

7. The melf/1.! ot cl.ti^ 6, uiten-itt `\;ti.l diimcyurtttte cotnpriaes lulu-.Lc dii-oe inte :1nd :it lez-st 2 equiyelents of ttilcoeynurttr :.ic prewnt [nr ctgtzivulent of ,"olyh).tlro ;y ntutericrl. i

Zt. 'the pro/:tss of cltlim 2 herein s.i.l tthylt-uiotlly unsztttuntct tnztiurlnl ix :n cthyluui-:zrllt' tun/.untitled yolymier hzivinu trout :about V5 to 5U mole percent uzttnruted diez-.lut xylie :und units und Loin about 5 to 5t :toll: iwf.

34. The cornpif n of'c -o wherein said polyhydroxy material comprises ir" 3 to l parts by weight 0 an csscmiully nnionzil lim-ur condensation polycslcr of :in aliphatic diczboxylic :ici-l :ri/ :in aliphatic glycol, said polyester havivg :i hydro-:yl number of 20 to 100, and from about 2 o 3 parts by gbl of polyixydroxy organic material having at lef-:t 3 hydroxyl groups comprising a condenviticr: polycscr of a polyhydiic alcohol having :u Icnfsf. 2 hyizaxyl gro-sgi, an aliphatic glycol and an aliphatic dicnrbo--x-llc acid.

3S. The compos ion of claim 34 wherein said polyhydroxy orgrnic confound having 1?. lcasr. 3 hydroxyl groups compines a condensation polyester of a polyhydric alcolici sclecal from lo .p consisting of trimclliylol propano :mi trimc ...l cilena, an aliphatic glycol sclccrcd from ille grou ronsisling of chylcne glycol and propylcn: glycol ami zn aliphatic dicarboxylic acid, wherein said pslycslcr km a ligglroxyl numb/:r of from about 120 to 21S.

36. The: composiiion of claim 34 wherein said diisccycrcin said tertiary BESTAVAlLABLE COPY ocygunc are prsrcn for cczl.- o

poly ,1y mncrial.

37. composiiion of claim 31 '..-I positie as dissolved in a non-reactive org:

ing no naive Zcrcwilizoil hydrogen group.

38. The composition of claim 31 whcrcin scid. prima: comprises a non-reactive pigment.

References Cited by ille Examizzc: UNITED STATES PATENTS 2,430,479 lI/llfl Pratt et al. 56-33 2,622,9U l2/l952 Seymour et al. 156-293 X 2,663,662 12/953 Graf ci al. 155-293 K 2,72l,l5';3 lil/1955 .olimion 15f-293 P2 2,769,325 ll/I956 Yoho 15G-331 )C 2,8%,932 7/1959 Bader ct al. IGI-214 X 2,953,439 9/1960 Young',

3,063,953 11,1962 Perkins et al. 156-2-31 'f 3,088,354 5/1963l Bonanni -U6-332 EARL E?. BERGERT, I n'mary Examiner.

UNITED STATES PATENT oEEICE CERTIFICATE OF CORRECTION Patent No. 3,219,516 November 23 David Stanley Cobbledick It is hereby certified that error appears in the above numbe ent requiring correction and that the Said Letters Patent should corrected below.

Column 2, line 67, for "wil" read will column 3,

line 14, for "polymerizale" read polymerizable -Y- line 59, for "fromed" read formed line 71, for "trial read triol column 6, lines 69 to 70, the formula should appear as shown below instead of as in the patent:

column 7, line 16, for "unsatruated" read unsaturated Column l0, line 2, for "if" read of line 34, for "bis-l-hydroxy" read bis-(l-hydroxy column l1, line 32, after "glazed" insert pipe column 15, line 9, after "is" insert a column 16, line 74, for "comprisse" read comprises n.

Signed and sealed this 20th day of September 1966.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

24. A BONDED MULTI-LAYER STRUCTURE INCLUDING A SUBSTRATE HAVING ON AT LEAST ONE SURFACE THEREOF A POLYURETHANE PRIMER LAYER, WHEREIN SAID POLYURETHANE IS THE REACTION PRODUCT OF AN ORGANIC POLYHYDROXY MATERIAL HAVING AN AVERAGE ACID NUMBER OF FROM 0 TO 10 AND AT LEAST 1.2 EQUIVALENTS OF ORGANIC POLYISOCYANATE PER EQUIVALENT OF ORGANIC POLYHYDROXY MATERIAL, WHEREIN SAID ORGANIC POLYHYDROXY MATERIAL COMPRISES AN ESSENTIALLY DIFUNCTIONAL LINEAR CONDENSATION POLYER HAVING A HYDROXYL NUMBER OF FROM 20 TO 100 SELECTED FROM THE GROUP CONSISTING OF POLYETHERS, POLYESTERS AND MIXTURES THEREOF, AN IN SITU ADDITION-POLYERIZED RESINOUS COMPOSITION BONDED TO SAID PRIMER LAYER, WHEREINN SAID IN SITU POLYMERIZED COMPOSITION COMPRISES THE REACTION PRODUCT OF A POLYETHYLENICALLY UNSATURATED MATERIAL AND A MONOETHYLENICALLY UNSATURATED MATERIAL SELECTED FROM THE GROUP CONSISTING OF MONOVINYLIDENE COMPOUNDS, HALF-ESTERS OF ALPHA,BETA-ETHYLENICALLY UNSATURATED DICARBOXYLIC ACIDS AND MIXTURES THEREOF, WHEREIN AT LEAST ONE OF SAID UNSATURATED MATERIALS CONTAINS ACTIVE ZEREWITINOFF HYDROGEN GROUPS. 